Molecular orbital calculation and spectroscopic study of the photochemical generation of Bis(2,2{prime}-bipyridine)rhodium(I) from Bis(2,2{prime}-bipyridine)(oxalato)rhodium(III)
- Yokohama City Univ., Seto, Kanazawa-ku (Japan)
- Tokyo Inst. of Technology, O-okayama, Meguro-ku (Japan)
A planar complex, [Rh(bpy){sub 2}]{sup +} (bpy=2,2{sup {prime}}-bipyridine), was obtained from [Rh(ox)(bpy){sub 2}]{sup +} (ox=oxalato) by photoirradiation. A rate constant k for the photoreaction was evaluated as 1 x 10{sup 8} s{sup {minus}1} in simple first-order kinetics, whereas a ligand dissociation, a reorganization of the coordinated bpy, and a two-electron transfer were involved in the reaction. The process of the Rh(I) complex generation was investigated in terms of a discrete variational(DV)-X{alpha} molecular orbital calculation on [Rh(ox)(HN=CHCH=NH){sub 2}]{sup +} instead of [Rh(ox)(bpy){sub 2}]{sup +}. From the calculation, using the transition-state method, it was predicted that a transition of the ox {pi}{sup *} orbital to the metal 4d{sub z}{sup 2} orbital caused the ligand dissociation and the reorganization of the coordinated bpy occurred in the ox {pi} to Rh 4d{sub x{sup 2}-y{sup 2}} excited state stabilized by the ox elimination. Upon release of the ligand and a change from octahedral to square-planar geometry, the electron density on the metal increased and the Rh 4d orbital acquired a d{sup 8} electronic configuration.
- OSTI ID:
- 274272
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 13 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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